Process for the production of complex alkali aluminum alkyls or alkali aluminum alkyl hydrides



United States Patent 15 Claims. (01. 260-448) This invention relates toa process for the production of complex alkali aluminum alkyls or alkalialuminum alkyl hydrides.

It is known that aluminum alkyls form complex compounds with varioussubstances. For example, such com plexes are formed from aluminum alkylsand ethers, thioothers or tertiary amines, but also from the organicaluminum compounds and alkali halides, more especially alkali fluorides,alkali cyanides, alkali hydrides and alkali alkyls. All these complexescan be produced by simple combination and perhaps also by joint heatingof the complex formers and aluminum alkyls. These complex aluminum alkylcompounds have acquired considerable industrial interest, for example aselectrolyte liquids in electrolysis processes, for example in therecovery of sodium by electrolysis or for the electrolytic production ofmetal alkyl compounds of the second to fifth groups of the PeriodicSystem and in particular for the electrolytic production of leadtetraalkyl compounds as described in the co-pending applications No.548,862, filed November 25, 1955, and issued as US. Patent No. 2,985,568on May 23, 1961, and 740,623, filed June 9, 1958, and issued as US.Patent No. 3,069,334 on December 18, 1962; as well as in the followingapplications which are now abandoned:

Serial No. 792,467, filed Feb. 11, 1959 Serial No. 792,614, filed Feb.11, 1959 Serial No. 27,218, filed May 5, 1960 Serial No. 27,219, filedMay 5, 1960 Serial No. 27,220, filed May 5, 1960 Among these compounds,it is more especially the complex compounds of aluminum trialkyl withalkali hydrides and alkali alkyls, i.e. the alkali aluminum trialkylhydrides, for example Na[Al(C H H] and alkali aluminum tetraalkyls, forexample Na [Al(C H which have achieved particular importance aselectrolytes, Whether for the precipitation of metallic sodium, or forthe electrolytic production of metal alkyls, for example for theproduction of lead tetraethyl. These two last mentioned groups ofcomplex compounds are hereinafter designated as alkali aluminum alkyls.

In the production of such metal alkyls by electrolysis, more especiallyfor obtaining lead tetraethyl, mixtures of metal alkyls and freealuminum trialkyl are formed as primary anodic electrolysis product.These mixtures must firstly be separated into aluminum trialkyl and thedesired metal alkyl and secondly it is essential in order that such anelectrolysis process may be conducted economically, for the freealuminum alkyl to be converted to the complex compound used aselectrolyte. In the simplest form, this reconversion of the aluminumtrialkyl is successfully achieved by direct reaction with sodium hydrideor sodium alkyl. In practise, however, a series of dififlculties arise.Thus, if the mixture to be reacted contains metal alkyl compoundssensitive to hydride, for example lead tetraethyl, the sodium hydridecannot be used for the complex formation, because otherwise this metalalkyl compound, that is to say, for example the lead tetraethyl, woulddecompose. A reaction with alkali alkyl is possible and can also becarried out practically. The exploitation of this possibility on a largeindustrial scale is however precluded by the fact that the alkali alkylscan only be prepared with difliculty, so that the provision of adequatequantities of alkali alkyls is only possible with practicaldifficulties, at least at the present time. The working up of theprimary electrolysis products is thus eilected by way of other complexcompounds of aluminum triethyl, but these compounds are not theaforementioned most important complex electrolytes.

Thus, for example, with the electrolytic production of lead tetraethyl,using an electrolyte of sodium-aluminum tetraethyl at the lead anode, amixture of 1 mol of lead tetraethyl and 4 mols of aluminum triethylisobtained. The lead tetraethyl can be separated out from this mixturein pure form by converting the aluminum triethyl into its complexcompounds with sodium fluoride and/ or sodium cyanide, as described inthe patent application 40,134, filed July 1, 1960, and now abandoned(.Process for Separating Aluminum Triethyl From Other Metal EthylCompounds). The lead tetraethyl is sparingly soluble in these compoundsand can be separated out in liquid form.

T he aluminum triethyl is thus a decomposition product of theelectrolyte used during the electrolysis. Consequently, if it is desiredto operate economically, it must be supplied to the electrolyte again inthe original form as sodium-aluminum tetraethyl. This can only beeiiected by the alkali fluoride or alkali cyanide complexes being againtransformed into sodium aluminum tetraethyl.

Hitherto, there has been 110 other possibility than the thermal crackingof the corresponding complexes in vacuo, as described in respect of thealkali fluoride complexes of aluminum alkyl, for example in Patent2,844,- 615. With such a thermal cracking process, free aluminumtrialkyl distils off and an alkali fluoride or alkali cyanide is left.In the case of the alkali fluoride complexes, this thermal cracking isonly successful up to the so-called 1:1 complex compounds, for exampleof the for mula NaF-AlR Thereafter, the free aluminum trialkyl which isdistilled 011 could be reconverted with sodium hydride and thecorresponding olefine or the alkali alkylene into the complex alkalialuminum alkyls. The disadvantage of this process is that the thermalcracking is comparatively diflicult and unpleasant. It is diflicult toavoid overheating and particular care and attention is necessary if itis desired to obviate losses due to decomposition. Furthermore, asalready indicated, the cracking only proceeds smoothly with thefluorides up to the 1:1 complex compounds. It follows from this that itis not possible simply to add alkali fluoride for separating out forexample the lead tetraethyl, if it is desired to recover all thealuminum triethyl, but the 1:1 complex compound itself must be used forthis purpose.

Another working up method for the said mixture of for example aluminumtriethyl and lead tetraethyl consists in treating the mixture with asuitable tertiary amine, more especially tributylamine, as described inUS. Patent 3,119,854, issued January 28, 1964 (Method of SeparatingAluminum Triethyl From Other Metal Ethyl Compounds and to a NovelAluminum Complex Compound). The tributylamine compound of aluminumtriethyl is solid at a sufficiently low temperature and it can beseparated out by the cooling of lead tetraethyl; the necessity thenexists of reconverting this tributylamine compound of the aluminumtriethyl into the original electrolyte (sodiumaluminum tetraethyl).Problems of similar nature frequently arise in the course of modernelectrolytic processes for the production of metal alkyls.

The complex compounds of the aluminum trialkyls I converted into amixture of sodium fluoride and aluminum triethy1-triethylamine.Conversely, the etherates of the aluminum trialkls, for example aluminumtriethyldiethyl etherate, can be split for example by potassium fluorideinto potassium fluoride complexes of aluminum triethyl and free ether.It is not possible in practise to formulate any laws which regulate thestability of the various aluminum alkyl complexes. It was not possibleto foresee how perhaps the sequence of the complex stability would hewhen comparing a series of substances which are capable of formingcomplexes.

The present invention is based on the unexpected and surprising factthat alkali hydrides in combination with the aluminum trialkyls, arestronger complex formers even than tertiary amines and the alkalifluorides and cyanides. It has surprisingly also been found that thesevery stable complexes can be split by alkali hydrides, the correspondingalkali aluminum alkyls then being formed.

Accordingly the present invention provides a process for the productionof alkali aluminum alkyls or alkali aluminum alkyl hydrides, whereinother aluminum trialkyl complex or addition compounds are reacted withalkali hydrides if desired in the presence-of oleflnes. Particularlysuitable starting materials for this reaction are the alkali halidecomplexes, more especially the alkali fluoride complexes of the aluminumtrialkyls, the alkali cyanide complexes and the trialkylamine additioncompounds of the aluminum trialkyls or mixtures containing thesecompounds.

In accordance with the invention the aluminum complexes can be splitwith alkali hydrides, if necessary in the presence of olefines. In thisembodiment of the invention it is the alkali aluminum alkyl complexeswhich are formed and not the aluminum alkyl hydride complex. It ispreferable to use an olefine which corresponds to the alkyl residue. Itis alsopreferred to use sodium hydride.

The complex formers originally combined in complex form with thealuminum alkyls and liberated by the alkali hydrides or alkali alkylscan be separated very easily from cially with aluminum triethyl, sodiumhydride not only forms a 1:1 complex, but also a 1:2 complex with thecomposition NaH-2Al(C H This complex has been proved to be more stablethan even the 1:1 complex of aluminum triethyl with sodium cyanide.Consequently, if 1 mol of sodium hydride is added to the compoundNaCN-2Al(C H sodium cyanide immediately precipitates. Sodium cyanide canalso be precipitated from the 2:1 complex of aluminum triethyl andsodium cyanide by adding the compound Na[Al(C H H]. In this second case,the complex compound of the sodium hydride with the aluminum triethyloperates approximately in the manner of a dissolved sodium hydride.

Even although the disadvantages of the thermal splitting of thecomplexes of aluminum trialkyl for recovering the free aluminum trialkylor the alkali aluminum tetraalkyl are largely obviated by the previouslydescribed embodiment of the invention, it is still also possible forcertain difliculties to arise in some cases using the above describedembodiment of the invention.

The direct treatment of the complex aluminum compounds with solidhydride is subject substantially to the general difficulty peculiar toall reactions in which, under the action of a solid substance on aliquid, the first solid substance disappears and a second solidsubstance is formed. Under such circumstances, incrustation of the firstsolid substance by the second substance being separated out can veryreadily occur, and this means that even if the main part of the reactionproceeds fairly quickly, a relatively long time may be necessary until acomplete conversion has taken place.

'In another embodiment of the invention, it is now possible alsocompletely to eliminate these ditficul-ties. In this embodiment use ismade of the differing complex strength of the diflerent aluminumtrialkyl complexes, but the initial complex compound is not directlytransformed into the alkali aluminum tetraalkyl complexes, but thereaction is carried out in stages, i.e. an intermediate reaction isinterposed. This intermediate reaction consists in initially adding tothe alkali aluminum alkyl halide or other complex aluminum compounds anether or a tertiary amine. Corresponding to the actual complexstabilities, an aluminum trialkyl etherate or an aluminum trialkyltrialkyl aminate is split off from the less stable initial complexaluminum compounds. Simultaneously, either the liberated inorganiccomplex former is directly obtained or the so-called 1:1 complexcompounds are obtained as second reaction component. For example, thecombination NaF-2Al(C H with triethylamine gives sodium fluoride andaluminum triethyltriethylaminate. From the corresponding combination ofthe compound KF-2Al(C I-I only 1 mol of aluminum triethyl is split offas triethylaminate, and the 1:1 compound KF-Al'(C H is obtained. Ethers,such as diethyletber, diisopropyl ether, di-sec.-butylether ordi-n-butylether, generally provide the 1:1 compounds as well as 1molecule of the corresponding etherates from the complex fluorides ofaluminum trialkyl. A condition for carrying out this form of the processis obviously that the complex initial aluminum compounds can be split byadding ether or tertiary amine. As already mentioned, predictions canscarcely be made here for the special case, but it is neverthelesspossible from ,case to case to establish easily, by a small initialexperiment, whether this form of the invention can be used.

If such a conversion takes place, it is then very easy to separate theseetherates or trialkyl aminates of the aluminum trialkyl from thecleavage products, and thereafter to convert them with alkali hydride oralkali hydride and olefine into the alkali aluminum alkyls whilesplitting off amine or ethers.

Thus, considered as a whole, even if this form of the process requiresan additional reaction stage, it can still provide considerableadvantages. The aluminum trialkyl etherates or aluminum trialkyltrialkylaminates are not solvents for alkali fluorides or cyanides. Evenif the cleavage extends to below these salts, it is only necessary topour off the liquid aluminum compounds from the solid phase or perhapsremove the said compounds by way of a filter candle. If the cleavageonly extends to the 1:1 compounds, the etherates or trialkylaminates canbe separated with extreme case by distillation, preferably a continuousvacuum distillation, from the complex 1:1 compounds. It is true thatdistillation is necessary, as with the thermal splitting, but it is nolonger a question of a splitting or cleavage of a complex compound, i.e.of the separation of free aluminum trialkyl from a dissociationequilibrium, which may be of the nature but simply of distilling off thealuminum trialkyl etherate or trialkyl aminate, which has already beencompletely formed, from its mixture with the 1:1 complex.

The second stage in this form of the process according to the invention,i.e. the final regeneration to the complex electrolytes, proceedsextremely quickly and easily, since it is now only necessary for thesodium hydride to dissolve during the reaction and no solid substance isseparated out during this reaction.

If the alkali halide complex compounds and the alkali hydride used forthe splitting or cleavage contain dilferent alkali metals the cleavagegenerally takes place in such a way that the alkali metal with thehighest atomic number remains in the alkali aluminum alkyl and thehalide of the alkali metal with the lower atomic number if separatedout.

As starting mate-rial for the process according to the invention, it ispreferred to employ aluminum trialkyl complex compounds which originatefrom the working up of the electrolysis products from the electrolyticproduction of metal alkyls, and it is in fact preferred to employaluminum trialkyl complex compounds which are free or substantially freefrom the metal alkyl compounds to be produced. The invention is furtherillustrated by the following examples:

Example 1 299 g. (:lmol) of aluminum triethyl tributylaminate are addedto 8 g. (=1 mol) of lithium hydride in a dry 500 cc. flask filled withnitrogen and the reaction mixture is heated while stirring to atemperature of from 100 to 200 C. Over a period of 1 hour, all thelithium hydride has been dissolved. The reaction mixture is heated undera vacuum of 1 mm. Hg to 100 C. (measured in the reaction mixture) andtri-n-butylamine distils off in a quantity of 180 g. (=0.97 mol). Thedistillation residue is 122 g. of pure lithium-aluminum trie thylhydride(:100% of the theoretical).

Example 2 150 cc. of a suspension of NaH in parafiin oil is added at 90C. and while stirring to 215 g. (:1 mol) of aluminumtriethyl-triethylaminate in a 500 cc. flask filled with nitrogen. Thecontent of sodium hydride in the suspension was fixed at 15.3 g. of NaHper 100 cc. of suspension. All the NaH is dissolved in a short time. Thereaction mixture is transferred under nitrogen into an autoclave with areaction chamber having a capacity of '1 litre and heated to 160 C.Ethylene is introduced at a pressure of substantially 10 atm. Thepressure in the autoclave is expediently kept constant by connecting thereaction vessel by way of a pressure-tight metal capillary tube to alarger storage vessel in which there is an ethylene pressure of 10 atm.Thorough mixing of the reaction components is assured by shaking theautoclave. Experience shows that the absorption of ethylene ceases afterabout 5 hours. In order to check this, the supply of ethylene is stoppedand it is observed whether there is any further decrease in pressure inthe sealed reaction vessel. The excess ethylene is blown off while hotand the liquid contents of the autoclave are emptied out under nitrogenor ethylene pressure while hot.

The reaction mixture is heated under a vacuum of 10 mm. Hg to 120 C., atotal of 100 g. (:1 mol) of triethylamine being distilled olf. Thereaction mixture consists of two immiscible liquid phases, of which thelower phase solidifies on cooling (M.'P. about 120 (3;). It ispractically pure sodium aluminum tetraethyl. The top phase is parafiinoil containing only a little sodiumaluminum tetraethyl and can beimmediately employed again for the preparation of a sodium hydridesuspension.

Example 3 0.95 mol of sodium hydride suspension in Decalin (400 g.NaH/kg. suspension) are added to 270 g. (:1 mol) of the sodiumfluoride-aluminum ethyl 1:2-compound at a temperature of from 80 to 100C. After 30 minutes, the sodium hydride has dissolved. The Decalin isremoved at 2 to 3 mm. Hg (bath temperature up to 120 C.), and themixture of sodium-aluminum triethyl hydride and sodium fluoride-aluminumtriethyl is obtained.

1 mol of sodium hydride (solid or in Decalin suspension) is initiallyadded to 1 mol of sodium fluoride-aluminum triethyl 1:2, as described inExample 3, then another 0.95 mol of sodium hydride is added, the mixtureis placed in a shaker-type autoclave and treated at 180 C. for more than20 hours with an ethylene pressure of 15 atm. After emptying out thecontents of the autoclave, these mixtures can be separated at C. in 2hours by settlement. The sodium-aluminum tetraethyl can be cleanlyseparated from the sodium fluoride which quickly settles on the bottom.After settlement, the Decalin can be first of all extracted as a toplayer above the sodium-aluminum tetraethyl and can be used again forpreparing a fresh sodium hydride suspension.

Example 5 2 mols of sodium hydride are added to 1 mol of sodiumcyanide-aluminum triethyl 1:2 at 120 C. while stirring. After 5 hours at120 C., the sodium hydride has dissolved and 1 mol of sodium cyanide hasseparated out. The sodium cyanide is removed from the sodiumaluminumtriethyl hydride by centrifuging and is washed with benzene to eliminatethe residues of organometallic substances.

Example 6 1.95 mols of sodium hydride are added to -1 mol of sodiumhydride-aluminum triethyl 1:2. The mixture is placed under nitrogenpressure in a 500 cc. autoclave.

In the stirrer-type autoclave, the mixture reacts at Crand an ethylenepressure of 15 atm. in 4 hours to sodium-aluminum tetraethyl. Thecontents of the autoclave can be separated at 150 C. and the puresodium-aluminum tetraethyl is extracted.

Example 7 1 mol of dry potassium hydride is added to 1 mol ofpotassium-aluminum tripropyl fluoride. and heated while stirring to 90C. After about 2 to 3 hours, potassium hydride is no longer present inthe solid phase and instead an equivalent quantity of KF hasprecipitated. The potassium fluoride precipitate is allowed to settle at90 C. and the clear supernatant liquid is siphoned off, this liquidbeing pure potassium-aluminum tripropyl hydride. The yield ofpotassium-aluminum tripropyl hydride is g. (:97% of the theoretical).

Example 8 As described in the preceding example, 1 mol ofpotassium-aluminum tri-n-octyl fluoride is reacted at 90 C. with 1 molof dry potassium hydride; The potassium hydride dissolves within a fewhours and the equivalent quantity of potassium fluoride is precipitated.The precipitate is allowed to settle and the supernatant liquid, whichis potassium-aluminum tri-n-octyl hydride, is siphoned off. The yieldofthis compound is 380 g. (=93% of the theoretical).

Example 9 2 g. (=1 mol) of sodium hydride are added to 257 g. (=1 mol)of aluminum triisobutyl trimethyl aminate in a dry reaction vesselfilled with nitrogen and gradually heated within approximately 2 hoursand while stirring to 50 to 60 C. until all the NaH has dissolved. Atthe rate atwhich the NaH is dissolved, trimethylamine is distilled oflfrom the reaction mixture, this triethylamine being condensed at 20 C.in a receiver cooled to a low temperature and connected to the reactionvessel. After all the trimethylamine has distiled off, the reactionmixture consists of sodium-aluminum triisobutyl-hydride.

- 7 The yield of this complex compound is 222 g. (:100% of thetheoretical) and the yield of trimethylamine is 55 g. (=93.5% of thetheoretical).

Example 1 2 mols of sodium hydride are added at 130 C. to 1 mol ofpotassium fluoride-aluminum triethyl 1:2 and stirred for 5 hours. 1 molof sodium fluoride is precipitated and this is separated out by allowingit to settle at 90 C. The supernatant mixture contains 1 mol ofpotassium-aluminum triethyl-hydride as well as 1 mol of sodium-aluminumtriethyl hydride.

Example 11 202 g. of dry triethylamine are carefully added whilestirring at room temperature to 270 g. of

The precipitated sodium fluoride is allowed to settle and it isseparated from the formed aluminum triethyl-triethylaminate bydecanting. The sodium fluoride can be washed with a little benzene andafter removing the last traces of benzene in vacuo, it can be obtainedin pure form with a yield of 100% of the calculated quantity, and inaddition there are obtained 220 g. of aluminum triethyl-triethylaminate,i.e. 98% of the theoretical. This is further processed in accordancewith Example 2.

Example 12 102 g. of diisopropylether are added at room temperature to270 g. of NaF-2Al(C H The homogeneous liquid mixture is thereafterheated in vacuo at mm. Hg to 100 to 130 C. (measured in the liquid) and220 g. of aluminum triethyl diisopropyl etherate distil off. Thedistillation residue consists of 156 g. of

NaAl (C H F The result remains the same if 204 g. of diisopropyl etherare used instead of 102 g. The 102 g. of diisopropyl ether can bedistilled ofi from the reaction mixture before it. is placed undervacuum. The further processing of the distillate is in accordance withExample 2. 102 g. of diisopropyl ether distil off during the heatingwith sodium hydride in paraffin oil.

Instead of diisopropyl ether, it is also possible to use diethyl ether,.but in this case the danger of an ether loss is greater than with thediisopropyl ether, which has a higher boiling point.

In this example, only half of the aluminum triethyl contained in the 270g. of NaF-2Al(C H is utilised. With the main use of the present process,which is perhaps the separation of lead tetraethyl and aluminumtriethyl, this is unimportant. It only means that 4 mols of NaF-Al(C Hand not two mols of NaF must be added to the mixture of Pb(C H ).,+4Al(CH Example 13 260 g. of di-n-butyl ether are carefully added at about 50C. to 277 g. of NaCN-2Al(C H Distillation is carried out at a pressureof 10 to 15 mm. from an oil bath, the temperature of which rises slowlyfrom 120 to 200 C. 470 to 480 g. of aluminum triethyl dibutyl etherateare obtained as distillate and 49 g. of solid sodium cyanide as residue.The distillate is further processed according to Example 2 anddibutylether appears instead of triethylamine. Otherwise, the entireprocedure is the same.

Example 14 286 gms. (:1 mol) of the compound K'F-2Al(C H are mixed at130 C. with 24 gms. (=1 mol) of sodium hydride (suspended in 200 ml. ofparafiinum liquidum) -while stirring. After minutes, all of the sodiumhydride has dissolved. The reaction mixture is treated for 4 hours at180 C. with ethylene of 15 atmospheres in a shaking autoclave of 1 litercapacity.

'2. Process for the production of alkali-metal-aluminum-tetra-al'kyl-complex compounds, which comprises reacting a complexof aluminum-trialkyl with a member selected from the. group consistingof alkali-metal-halides, alkali-metal-cyanides, and trialkyl amines,with an alkali metal hydride and reacting the resulting product with anolefin, and recovering the alkali-metal-aluminumtetraalkyl compoundformed.

3. Process for the production of alkali-metal-tetraalkyl-complexcompounds, which comprises the step-s of (1) reacting a complex ofaluminum-trialkyl with a member selected from the group consisting ofalkylmetal-halides, alkali-metal-cyanides, and trialkyl amines,

I :with an alkali metal hydride to thereby obtain an alkalimetal-alkyl-aluminum-hydride, thereafter (2) reacting the lattercompound with olefin, and recovering the alkalimetal-aluminum-tetraalkylcompound formed.

4. Process according to claim 2, wherein said complex alkali metalhydride and said olefin are contacted in a reaction zone and saidreactions occur simultaneously.

5. Process according to claim 1, in which the startingaluminum-trialkyl-complex compound is in the form of a complex with analkali-metal-halide.

6. Process according to claim 5, in which the startingaluminurn-t-riethyl-complex compound is in the form of a complex with analkali-metal-fluoride.

. 7. Process according to claim 1, in which the starting'aluminum-trialkyl-complex compound is in the form of .a complex with analkali-metal-cyanide.

8. Process according to claim 1, in which the startingaluminum-trialkyl-cornplex compound is in the form of a complex with atrialkyl-amine.

9. Process according to claim 1 which comprises effecting said reactionwith stoichiometric amounts of said aluminum-trialkyl-complex andalkali-metal-hydride reactants.

10. Process for the production ofalkali-metal-alurninum-alkyl-hydride-complex compounds, which comprisesreacting a complex of aluminum-trialkyl with a member selected from thegroup consisting of alkali-metal-halides and alkali-metal-cyanides witha member selected from the group consisting of ethers and tertiaryamines, to form the corresponding trialkyl-aluminum-complex with thesecond-mentioned member, and thereafter reacting the latter with analkali-metal-hydride, and recovering thealkali-metal-aluminum-alkyl-hydride compound formed.

11. Process according to claim 10, wherein a tertiary amine is reactedwith the first-mentioned complex to form aluminum trialkyl aminate andliberate a compound selected from the group consisting of alkali metalhalides and alkali metal cyanides, said tertiary amine is separated fromthe liberated compound and is thereafter reacted with said alkali metalhydride.

9 the latter with an alkali-metal-hydride and an olefin, and recoveringthe alkali-metal-aluminum-tetraalkyl compound formed.

13. In the process for separating mixtures of aluminum-trialkyl andother metal-alkyl compounds of the second to fifth group of the PeriodicSystem by treating the mixture with an alkali-metal-halide, wherebythere is formed a complex of the aluminumatrialkyl with said alkali-metal-halide, and separating the complex thus formed from themetal-alkyl, the improvement which comprises reacting thealuminum-trialkyl-alkali-halide-complex with an alkali-metal-hydride andan olefin, to form an alkalimetal-aluminum-tetraalkyl complex.

14. Process according to claim 13, wherein the mixture 10 metal-alkylcompound of the second to fifth group of the Periodic System.

15. Process of claim 12 wherein the first-mentioned complex is NaF-2Al(CH and said complex is reacted with an ether to form NaF-Al(C H and thealuminum triethyl etherate, and the etherate is separated from theNaF-Al(C H and the separated etherate is reacted with the alkali metalhydride and an olefin.

References Cited by the Examiner UNITED STATES PATENTS 2,786,860 3/1957Ziegler et al 260448 2,915,541 12/1959 .Ziegler et -al 260448 to beseparated consists of aluminum-triethyl and another 15 TO-BIAS E. LEVOW,Primary Examiner.

1. PROCESS FOR THE PRODUCTION OFALKALI-METAL-ALUMINUM-ALKYL-HYDRIDE-COMPLEX COMPOUNDS, WHICH COMPRISESREACTING COMPLEX OF ALUMINUM-TRIALKYL WITH A MEMBER SELECTED FROM THEGROUP CONSISTING OF ALKALI-METAL-HALIDES, ALKALI-METAL-CYANIDES, ANDTRIALKYL AMINES, WITH AN ALKALIMETAL-HYDRIDE, AND RECOVERING THEALKALI-METAL ALUMINUMALKYL HYDRIDE-COMPOUND FORMED.
 2. PROCESS FOR THEPRODUCTION OF ALKALI-METAL-ALUMINUM-TETRA-ALKYL-COMPLEX COMPOUNDS, WHICHCOMPRISES REACTING A COMPLEX OF ALUMINUM-TRIALKYL WITH A MEMBER SELECTEDFROM THE GROUP CONSISTNG OF ALKALI-METAL-HALIDES ALKALI-METAL-CYANIDES,AND TRIALKYL AMINES, WITH AN ALKALI METAL HYDRIDE AND REACTING THERESULTING PRODUCT WITH AN OLEFIN, AND RECOVERING THEALKALI-METAL-ALUMINUMTETRAALKYL COMPOUND FORMED.